CN113979426A - Phosphoric acid grafted nano onion carbon and preparation method and application thereof - Google Patents
Phosphoric acid grafted nano onion carbon and preparation method and application thereof Download PDFInfo
- Publication number
- CN113979426A CN113979426A CN202111387035.1A CN202111387035A CN113979426A CN 113979426 A CN113979426 A CN 113979426A CN 202111387035 A CN202111387035 A CN 202111387035A CN 113979426 A CN113979426 A CN 113979426A
- Authority
- CN
- China
- Prior art keywords
- cnos
- onion carbon
- nano onion
- preparation
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses phosphoric acid grafted nano onion carbon and a preparation method and application thereof, wherein nano onion carbon obtained by nano diamond high-temperature annealing is used as a raw material, and a mixed acid oxidation reaction of sulfuric acid and nitric acid is adopted to generate carboxylated nano onion carbon; mixing the onion powder with phytic acid, and carrying out high-temperature hydrothermal reaction to obtain the phosphoric acid grafted nano onion carbon. The preparation method is simple, the obtained product is quasi-spherical particles formed by a plurality of graphite layers, the average size is 5nm, and the product can be used for ion exchange materials, and is particularly suitable for nano-fillers in proton exchange membranes.
Description
Technical Field
The invention belongs to the technical field of environment functional materials, and particularly relates to phosphoric acid grafted nano onion carbon and a preparation method and application thereof.
Background
Nano onion carbon (also called carbon nano onion, CNOs) is a typical zero-dimensional nanomaterial, and has attracted research interest in recent years. Due to its unique structural properties, such as the presence of a large number of pores and defects in the graphite layer of onion-like structure, ultra-small size, large specific surface area, and good chemical stability, research has been conducted in many fields, such as electronics, catalysis, sensors, energy storage and conversion. Due to the high specific surface area and intermolecular forces, surface functionalized CNOs have good dispersibility and negligible agglomeration. Furthermore, functionalized CNOs have good chemical and mechanical stability, high conductivity and adjustable surface structure, which makes them suitable for electrode materials in supercapacitors and adsorbents in environmental remediation. However, the study of functionalized CNOs as a filler in proton exchange membranes has been less common. In the first literature (Journal of Membrane Science 640(2021)119823), on the basis of synthesizing CNOs, high-density sulfonated CNOs are successfully prepared through phenylation and sulfonation reaction, and a series of composite membranes are prepared through compounding with polyarylethersulfones, wherein the composite membranes have good chemical stability and battery performance. However, in the method, because the surface of the CNOs is grafted with sulfonic acid groups, the CNOs serving as a strong acid can volatilize protons at high temperature, and the CNOs serving as a strong acid has poor water retention under low humidity, which is not beneficial to further improving the performance of the proton exchange membrane. Therefore, it is necessary to develop a novel structure and a synthetic method for preparing a modified inorganic nanomaterial with higher water retention capacity.
Disclosure of Invention
The invention aims to provide phosphoric acid grafted nano onion carbon, a preparation method and application thereof, which are used as inorganic fillers in proton exchange membranes and improve the comprehensive performance of composite membranes.
CNOs are prepared by thermal annealing. Firstly, putting a certain amount of nano diamond powder (NDs, 3-7nm) into a tube furnace in a nitrogen atmosphere, and then respectively heating the NDs to 1650-1700 ℃ at a certain heating rate. Keeping the temperature for 1h, cooling to room temperature at a cooling speed of 5 ℃/min, and then treating in air at 500 ℃ for 0.5-1 h to remove residual amorphous carbon. Finally, CNOs powder is obtained by recovery.
The CNOs are used as raw materials, and the technical solution for realizing the purpose of the invention is as follows:
(1) preparation of carboxylated nano onion carbon C-CNOs:
adding concentrated H with the mass concentration of 97-99% into a reaction container2SO4Adding nano onion carbon CNOs under stirring; stirring for 24 hours at room temperature;
slowly adding mixed acid of concentrated sulfuric acid and concentrated nitric acid into a reaction container, heating and stirring;
pouring into ice water after the reaction is finished, and then filtering, washing and drying to obtain C-CNOs;
(2) preparation of phosphorylated nano onion carbon P-CNOs:
dispersing C-CNOs in pure water, adding phytic acid, and performing ultrasonic treatment to gradually change the color of the solution from light brown to dark brown; adding the mixture into a reaction kettle, and heating;
after the reaction is finished, naturally cooling to room temperature, centrifugally separating, cleaning, freezing and drying to obtain the P-CNOs.
The preparation method comprises the following steps:
step 1, preparation of carboxylated nano onion carbon C-CNOs
Adding a certain amount of concentrated H into a three-neck flask provided with a magnetic stirring and constant pressure dropping funnel2SO4(97-99%) a certain amount of CNOs was added with stirring. The CNOs and concentrated sulfuric acid are fully contacted after stirring for 24h at room temperature. A certain amount of mixed acid of concentrated sulfuric acid and concentrated nitric acid is weighed and placed in a constant-pressure separating funnel, and the mixed acid is dropwise added into a three-neck flask. Heating the temperature from 30 ℃ to 80 ℃ at a heating rate of 3 ℃/min, and stirring and reacting for 1-2 h at the temperature of 80 ℃. And then pouring the solution into 200mL of ice water, filtering, washing twice with deionized water, then washing with an ethanol solution until the pH value of an effluent is neutral, and drying for 12h in vacuum at 80 ℃ to obtain the C-CNOs product.
Step 2, preparation of phosphorylated nano onion carbon P-CNOs
Dispersing a certain amount of C-CNOs in pure water, adding a certain amount of phytic acid, and carrying out ultrasonic treatment for 0.5-1 h, wherein the color of the solution gradually changes from light brown to dark brown in the process. The mixture was then added to a 50mL teflon lined autoclave and held at 180 ℃ for 12 h. Naturally cooling to room temperature, centrifugally separating, washing with ethanol and water once respectively, and freeze-drying for 24h to obtain the P-CNOs product.
Further, the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid in the mixed acid in the step 1 is 1: 2.5-3.0, wherein the mass concentrations of the concentrated nitric acid and the concentrated sulfuric acid are respectively 68% and 98%.
The concentration of the C-CNOs in the water in the step 2 is 2.0-2.5 mg/L, and the solid-to-liquid ratio of the C-CNOs powder to the phytic acid is 1: 20-25 g/mL.
The ion exchange capacity of the P-CNOs prepared by the method is 1.65-1.80 mmol/g.
The P-CNOs prepared by the method is used as a filler in a polymer electrolyte membrane, and the maximum output power of the assembled fuel cell at 60% low relative humidity (60% RH) is 85-110% higher than that of an unmodified polymer electrolyte membrane.
Compared with the prior art, the invention has the following remarkable advantages:
(1) according to the method, the nano diamond is used as a raw material, and the prepared phosphorylated nano onion carbon has a high specific surface area and a mesoporous structure, so that the water retention and ion exchange capacity of the membrane are improved;
(2) the carbon surface of the nano onion is grafted with a large amount of phosphate groups, and the phosphate groups are medium-strong acids, contain proton donors and acceptors, are easy to form hydrogen bonds, have obvious proton polarization effect, are doped into a polymer film, are favorable for improving the water absorption and the conductivity of the film, and particularly improve the battery performance of the polymer electrolyte film under the low humidity condition;
(3) the modified material of the phosphoric acid grafted nano onion carbon is phytic acid, and the raw material has wide sources and is distributed in crops and agricultural and sideline products, thereby being beneficial to environmental protection and human health.
Drawings
FIG. 1a is an HRTEM image of CNOs of example 1;
FIG. 1b is a HRTEM image of P-CNOs of example 1;
FIG. 2 is an IR spectrum of CNOs, C-CNOs and P-CNOs of example 1;
FIG. 3 is an XPS spectrum of CNOs and P-CNOs of example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings.
A preparation method of phosphoric acid grafted nano onion carbon takes NDs as a raw material, CNOs is prepared by a thermal annealing method, and then the CNOs reacts with mixed acid of sulfuric acid and nitric acid to generate C-CNOs; and finally, mixing the mixture with phytic acid, carrying out hydrothermal reaction, and carrying out centrifugation, washing and freeze drying to obtain the P-CNOs. The ion exchange capacity of the prepared P-CNOs is 1.65-1.80 mmol/g, and the P-CNOs is added into a sulfonated polyarylethersulfone polymer to prepare the composite membrane. In the polymer film, on one hand, the introduced P-CNOs inorganic nanoparticles have high specific surface area and mesoporous structure, so that the hydrophilicity and compatibility of the film are improved; on the other hand, a large number of phosphate groups are grafted on the surfaces of the P-CNOs, and can form hydrogen bond interaction with sulfonic acid groups of the sulfonated polyarylethersulfone, so that more active sites are provided for proton transfer, and the phosphate groups are medium-strong acids, and have the advantages of proton donors and acceptors, obvious proton polarization, high hydration energy and the like, so that the composite membrane shows more excellent comprehensive performance.
Example 1
(1) Preparation of nano onion carbon CNOs
2.0g of nano diamond powder (NDs, 3-7nm) is put into a tube furnace in a nitrogen atmosphere, and then the NDs are heated to 1650-1700 ℃ at a certain heating rate respectively. Keeping the temperature for 1h, cooling to room temperature at a cooling speed of 5 ℃/min, and then treating in air at 500 ℃ for 0.5-1 h to remove residual amorphous carbon. Finally, 1.62g of CNOs powder was recovered. FIG. 1a is an HRTEM image of CNOs (a); fig. 2 includes an infrared spectrum of CNOs; figure 3 includes CNOs XPS spectra.
(2) Preparation of carboxylated nano onion carbon C-CNOs
In a three-neck flask equipped with a magnetic stirring, constant pressure dropping funnel, 25mL of concentrated H was added2SO4(97-99%) with stirring0.4g of CNOs were added with stirring. The CNOs and concentrated sulfuric acid are fully contacted after stirring for 24h at room temperature. 25mL of concentrated sulfuric acid and 20mL of concentrated nitric acid are weighed into a constant-pressure separating funnel and are dropwise added into a three-neck flask. Heating the temperature from 30 ℃ to 80 ℃ at a heating rate of 3 ℃/min, and stirring and reacting for 1-2 h at the temperature of 80 ℃. Then pouring the solution into 200mL of ice water, filtering, washing twice with deionized water, then washing with ethanol solution until the pH value of effluent is neutral, and drying in vacuum at 80 ℃ for 12h to obtain 0.36g of C-CNOs product.
(3) Preparation of phosphorylated nano onion carbon P-CNOs:
in the aqueous dispersion of C-CNOs (2.0mg/L, 35mL), 1.4mL phytic acid is added, and ultrasonic treatment is carried out for 0.5-1 h, wherein the color of the solution gradually changes from light brown to dark brown. The mixture was then added to a 50mL teflon lined autoclave and held at 180 ℃ for 12 h. Naturally cooling to room temperature, centrifugally separating, washing with ethanol and water once respectively, and freeze-drying for 24h to obtain 0.05g of P-CNOs product.
FIG. 1b is a HRTEM image of P-CNOs; FIG. 2 includes IR spectra of C-CNOs and P-CNOs; FIG. 3 includes XPS spectra of P-CNOs.
Example 2
(1) Same as in example 1.
(2) Preparation of carboxylated nano onion carbon C-CNOs:
26mL of concentrated H was added to a three-necked flask equipped with a magnetically stirred, constant pressure dropping funnel2SO4(97-99%) 0.4g of CNOs are added with stirring. The CNOs and concentrated sulfuric acid are fully contacted after stirring for 24h at room temperature. 30mL of concentrated sulfuric acid and 20mL of concentrated nitric acid are weighed into a constant-pressure separating funnel and are dropwise added into a three-neck flask. Heating the temperature from 30 ℃ to 80 ℃ at a heating rate of 3 ℃/min, and stirring and reacting for 1-2 h at the temperature of 80 ℃. Then pouring the solution into 200mL of ice water, filtering, washing twice with deionized water, then washing with ethanol solution until the pH value of effluent is neutral, and drying in vacuum at 80 ℃ for 12h to obtain 0.38g of C-CNOs product.
(3) Preparation of phosphorylated nano onion carbon P-CNOs:
in the aqueous dispersion of C-CNOs (2.0mg/L, 30mL), 1.4mL phytic acid is added, and ultrasonic treatment is carried out for 0.5-1 h, wherein the color of the solution gradually changes from light brown to dark brown. The mixture was then added to a 50mL teflon lined autoclave and held at 180 ℃ for 12 h. Naturally cooling to room temperature, centrifugally separating, washing with ethanol and water once respectively, and freeze-drying for 24h to obtain 0.06g of P-CNOs product.
Example 3
(1) Same as in example 1.
(2) Preparation of carboxylated nano onion carbon C-CNOs:
20mL of concentrated H was added to a three-necked flask equipped with a magnetically stirred, constant pressure dropping funnel2SO4(97-99%) 0.4g of CNOs are added with stirring. The CNOs and concentrated sulfuric acid are fully contacted after stirring for 24h at room temperature. 40mL of concentrated sulfuric acid and 20mL of concentrated nitric acid are weighed into a constant-pressure separating funnel and are dropwise added into a three-neck flask. Heating the temperature from 30 ℃ to 80 ℃ at a heating rate of 3 ℃/min, and stirring and reacting for 1-2 h at the temperature of 80 ℃. Then pouring the solution into 200mL of ice water, filtering, washing twice with deionized water, then washing with ethanol solution until the pH value of effluent is neutral, and drying in vacuum at 80 ℃ for 12h to obtain 0.38g of C-CNOs product.
(3) Preparation of phosphorylated nano onion carbon P-CNOs:
in the aqueous dispersion of C-CNOs (2.2mg/L, 35mL), 1.92mL phytic acid is added, and ultrasonic treatment is carried out for 0.5-1 h, wherein the color of the solution gradually changes from light brown to dark brown. The mixture was then added to a 50mL teflon lined autoclave and held at 180 ℃ for 12 h. Naturally cooling to room temperature, centrifugally separating, washing with ethanol and water once respectively, and freeze-drying for 24h to obtain 0.05g of P-CNOs product.
Example 4
Preparation of P-CNOs doped electrolyte membranes (SPAES-1 wt% P-CNOs) and Fuel cell Performance:
0.8g of sulfonated polyarylethersulfone SPAES with a sulfonation degree of 45% is dissolved in 13.5mL of N, N-dimethylformamide (DMAc), stirred for 24h at normal temperature to obtain a mixed solution A, meanwhile, 80mg of P-CNOs powder prepared in example 1 is dissolved in 3.5mL of DMAc, subjected to ultrasonic treatment for 1h, stirred for 12h at normal temperature to obtain a solution B, the solution A and the solution B are blended, and stirred for 24h at normal temperature to obtain a casting solution. Slowly pouring the casting film liquid into an ultra-horizontal film casting disc, and heating the film casting oven at the temperature of (60 ℃, 4h → 80 ℃, 12h → 100 ℃ and 2 h). And taking out the composite membrane, soaking the composite membrane in 1mol/L hydrochloric acid solution for 72h, and then cleaning the composite membrane with deionized water to be neutral to obtain the composite membrane SPAES-1 wt% P-CNOs.
And (3) carrying out performance test on the prepared composite membrane: the IEC of the composite membrane SPAES-1 wt% P-CNOs reaches 1.52mmol/g, and the conductivity in water at 90 ℃ reaches 160.8 mS/cm. At H2/O2In the fuel cell test, under the conditions of 80 ℃ and 60% RH, the maximum output power of the cell is 370mW/cm, which is higher than that of the undoped SPAES membrane by 85%.
Claims (7)
1. The preparation method of the phosphoric acid grafted nano onion carbon is characterized by comprising the following steps of:
(1) preparation of carboxylated nano onion carbon C-CNOs:
adding concentrated H with the mass concentration of 97-99% into a reaction container2SO4Adding nano onion carbon CNOs under stirring; stirring for 24 hours at room temperature;
slowly adding mixed acid of concentrated sulfuric acid and concentrated nitric acid into a reaction container, heating and stirring;
pouring into ice water after the reaction is finished, and then filtering, washing and drying to obtain C-CNOs;
(2) preparation of phosphorylated nano onion carbon P-CNOs:
dispersing C-CNOs in pure water, adding phytic acid, and performing ultrasonic treatment to gradually change the color of the solution from light brown to dark brown; adding the mixture into a reaction kettle, and heating;
after the reaction is finished, naturally cooling to room temperature, centrifugally separating, cleaning, freezing and drying to obtain the P-CNOs.
2. The method for preparing phosphoric acid grafted nano onion carbon according to claim 1, wherein the heating and stirring in step (1) is carried out at a heating rate of 3 ℃/min to 80 ℃, and the stirring reaction is continued at a temperature of 80 ℃ for 1-2 hours.
3. The preparation method of phosphoric acid grafted nano onion carbon according to claim 1, wherein the ultrasonic treatment in the step (2) is carried out for 0.5-1 h; heating to 180 ℃ and reacting for 12 h.
4. The method for preparing phosphoric acid grafted nano onion carbon according to claim 1, wherein the volume ratio of concentrated nitric acid to concentrated sulfuric acid in the mixed acid in the step (1) is 1: 2.5-3.0, wherein the mass concentrations of the concentrated nitric acid and the concentrated sulfuric acid are respectively 68% and 98%.
5. The method for preparing phosphoric acid grafted nano onion carbon according to claim 1, wherein the C-CNOs of step (2) are dispersed in pure water, and the concentration of the C-CNOs in water is 2.0-2.5 mg/L; the solid-liquid ratio of the C-CNOs to the phytic acid is 1: 20-25 g/mL.
6. The phosphoric acid grafted nano onion carbon, which is obtained by the preparation method of any one of claims 1 to 5.
7. The use of the phosphoric acid grafted nano onion carbon as claimed in claim 1, which is used as a filler for preparing a polymer electrolyte membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111387035.1A CN113979426B (en) | 2021-11-22 | 2021-11-22 | Phosphoric acid grafted nano onion carbon and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111387035.1A CN113979426B (en) | 2021-11-22 | 2021-11-22 | Phosphoric acid grafted nano onion carbon and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113979426A true CN113979426A (en) | 2022-01-28 |
| CN113979426B CN113979426B (en) | 2023-10-20 |
Family
ID=79749773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111387035.1A Active CN113979426B (en) | 2021-11-22 | 2021-11-22 | Phosphoric acid grafted nano onion carbon and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113979426B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975698A (en) * | 2022-11-30 | 2023-04-18 | 潍柴动力股份有限公司 | Lubricating oil additive containing chemical surface modification nano onion carbon material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106660786A (en) * | 2014-09-16 | 2017-05-10 | 南洋理工大学 | Method of functionalizing surfaces of carbon nanomaterials |
| CN111115617A (en) * | 2019-12-24 | 2020-05-08 | 谢春艳 | Large-scale preparation method of high-purity hollow carbon nano-onion |
| CN113023727A (en) * | 2021-03-18 | 2021-06-25 | 青岛科技大学 | Preparation method of nano onion carbon |
| CN113604151A (en) * | 2021-08-27 | 2021-11-05 | 齐齐哈尔大学 | Preparation method of phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating |
-
2021
- 2021-11-22 CN CN202111387035.1A patent/CN113979426B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106660786A (en) * | 2014-09-16 | 2017-05-10 | 南洋理工大学 | Method of functionalizing surfaces of carbon nanomaterials |
| CN111115617A (en) * | 2019-12-24 | 2020-05-08 | 谢春艳 | Large-scale preparation method of high-purity hollow carbon nano-onion |
| CN113023727A (en) * | 2021-03-18 | 2021-06-25 | 青岛科技大学 | Preparation method of nano onion carbon |
| CN113604151A (en) * | 2021-08-27 | 2021-11-05 | 齐齐哈尔大学 | Preparation method of phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975698A (en) * | 2022-11-30 | 2023-04-18 | 潍柴动力股份有限公司 | Lubricating oil additive containing chemical surface modification nano onion carbon material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113979426B (en) | 2023-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110492081B (en) | Preparation method and application of cobalt selenide/zinc selenide @ nitrogen-doped porous carbon nanotube | |
| CN108232209B (en) | Medium-temperature carbonized metal skeleton compound hole expanding technology for preparing high-activity iron-nitrogen-carbon catalyst | |
| CN106252628B (en) | A kind of preparation method of manganese oxide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery | |
| CN109616671B (en) | Method for preventing intermetallic compound from agglomerating and growing up at high temperature and application | |
| CN106876759A (en) | Modified polymer hybrid PEM of the bar-shaped metal organic framework of amino functional and preparation method thereof | |
| CN106046404B (en) | NafionTMModifiedTwo-dimensional layered material nanosheet-polymer hybrid proton exchange membrane and preparation method thereof | |
| CN109569670B (en) | Preparation method of BiOBr/black phosphorus alkene heterojunction nano composite material | |
| CN106910894A (en) | A kind of preparation method of mesoporous nano carbon microspheres graphene interlayers composite | |
| CN113942995A (en) | Heteroatom-doped porous carbon material and preparation method and application thereof | |
| CN113979426B (en) | Phosphoric acid grafted nano onion carbon and preparation method and application thereof | |
| CN113813975A (en) | ZIF-8 derived hierarchical pore M-N-C catalyst and preparation method thereof | |
| CN106299392A (en) | A kind of nanometer Mn with manganese defect3o4and preparation method thereof and application in electrocatalytic oxidation reduction reaction | |
| CN112086672A (en) | Composite high-temperature proton exchange membrane for fuel cell and preparation method and application thereof | |
| KR101419340B1 (en) | Preparation method of Graphite oxide and graphene nanosheet | |
| CN103641101A (en) | Two-dimensional structural carbon nanomaterial and preparation method thereof | |
| CN114373971B (en) | Preparation method of proton exchange membrane blended by perfluorinated sulfonic acid resin and Ce-MOF | |
| CN110407208A (en) | A kind of preparation method of mesoporous graphene-based charcoal-aero gel | |
| CN114031870B (en) | Proton exchange membrane and preparation method and application thereof | |
| CN112079348B (en) | Preparation method and application of graphene/MOF derived sulfide composite aerogel | |
| CN110127669B (en) | Preparation method of reduced graphene oxide and trimanganese tetroxide nanoparticle hybrid aerogel | |
| CN113637131A (en) | Perfluoroalkyl chain modified covalent organic framework, preparation method and application thereof | |
| CN114171740A (en) | Preparation method of nano lithium iron phosphate cathode material and lithium ion battery | |
| CN112086673A (en) | Composite high-temperature proton exchange membrane for fuel cell and preparation method thereof | |
| CN112934011A (en) | For CO2Separated membrane material and preparation method thereof | |
| CN113120955B (en) | Preparation method of grafted sulfonated butyl titanium dioxide nanotube |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |